Olefin polymerization catalysts



drides.

United States Patent 3,242,099 OLEFIN POLYMERIZATION CATALYSTS Robert M.Manyik, St. Albans, Wellington E. Walker and Thomas P. Wilson,Charleston, and George F.

Hurley, St, Albans, W. Va., assignors to Union Carbide Corporation, acorporation of New York No Drawing. Filed Mar. 27, 1964, Ser. No.355,448

16 Claims. (Cl. 252429) This application is a continuation-in-part of anapplication entitled Olefin Polymerization, Serial No. 72,584, filed onNovember 30, 1960, now abandoned.

This invention relates to the polymerization of monounsaturatedalphaolefins. More particularly, it is concerned with a new catalyticprocess for the polymerization of said olefins and with the catalystcomplexes per se.

It is well known that mono-unsaturated alpha-olefins can be polymerizedwith a catalyst composition consisting of a mixture of two components.In these known catalyst compositions the two components are a compoundof a transition metal of Groups IVA, VA, and VIA, and a compound of ametal of Groups IA, HA, and 11113 of the Periodic Chart of the Atoms Thecompounds of the metals of Groups IA, IIA, and IIIB can be the organometallic compounds, the organo metallic halide compounds, the organometallic hydrides, or the metal hy- The Periodic Chart referred to isthe1956 Edition published by W. M. Welch Manufacturing Company, Chicago,Illinois.

It has now been found that mono-unsaturated alphaolefins can bepolymerized to produce solid high molecular Weight polymers bycontacting them with a catalyst complex as hereinafter set forth. Thecatalyst complexes of this invention can comprise the complex obtainedfrom two components or the complex obtained from three components.

In the embodiment wherein two components are pres ent, the twocomponents used to produce the catalyst complex are 1) thepoly(hydrocarbylaluminum oxides) and (2) the transition metal compoundsof the metals of Groups IVA, VA, and VIA. In that embodiment whereinthree components are present, the three components making up thecatalyst complex of this invention are (1) the poly(hydrocarbylaluminumoxides), (2) the transition metal compounds of the metals of Groups IVA,VA, and VIA, and (3) a compound of the metals of Groups IA, IIA, andIIIB of the Periodic Chart of the Atoms.

The poly(hydrocarbylaluminum oxide) used as a component for the catalystcomplex in this invention consists essentially of units which can berepresented by the general formula:

R ital L I wherein R represents an alkyl radical containing from 1 toabout 12 carbon atoms, or an aryl radical, for example, phenyl,phenethyl, methoxyphenyl, benzyl, toly-l, xylyl, naphthyl, naphthal,methylnaphthyl, and the like. Among the alkyl radicals which R canrepresent one can mention methyl, ethyl, propyl, isopropyl, butyl,isobutyl, t-butyl, pentyl, neopentyl, hexyl, Z-methylpentyl, heptyl,ootyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl,isodecyl, undecyl, dodecyl, and the like.

Illustrative of the suitable poly(hydrocarbylaluminum oxides) arepoly(methylaluminum oxide), poly(ethylaluminum oxide),poly(isopropylaluminum oxide), poly(nbutylaluminum oxide),poly(isobutylaluminum oxide), poly(decylaluminum oxide),poly(dodecylaluminum oxide), poly(benzylaluminum oxide),poly(phenylaluminum oxide), poly(tolylaluminum oxide), poly(naphthylicealuminum oxide), poly(ethylnaphthylaluminum oxide), and the like.

The poly(hydrocarbylaluminum oxides) are produced by the reaction ofwater with an organo hydrocarbylaluminum compound which contains atleast one hydrocarbyl radical attached to the aluminum atom. The termhydrocarbyl as used in this application represents a. saturated alkylgroup or an aryl radical, as defined above. The reaction of water withthe organo hydrocarbylaluminum compound is preferably carried out byadding the water to a solution of the organo hydrocarbylaluminumcompound in an anhydrous, inert, organic solvent. The concentration ofthe organo hydrocarbylaluminum compound in the solvent can vary fromabout 5 percent by weight or less to as high as about percent by Weightor more. Suitable organic solvents are, among others, the saturatedaliphatic compounds, for example, hexane, heptane, pentane, isooctane,purified kerosene, et cetera; the cycloaliphatics such as cyclopentane,cyclohexane, methylcyclopentane, dimethylcyclopentane, et cetera; thearomatic solvents such as benzene, toluene, xylene, et cetera, and thelike. The only requirement in the selection of the inert organic solventis that it be liquid at the reaction temperature and that it does notreact with the water or the organo hydrocarbylaluminum compound charged,or interfere with the reaction in any way whatsoever.

The organo hydrocarbylaluminum compounds suitable for use as startingmaterials in the preparation of the poly(hydrocarbylaluminum oxides) arerepresented by the general formula:

wherein R has the same meanings as previously defined and R representsan alkyl radical containing from 1 to about 12 carbon atoms, an arylradical, or a hydrogen atom.

The hydrocarbylaluminum compounds which can be used in the reaction withWater to produce the poly(hydrocarbylaluminum oxide) are those having acarbonto aluminum bond. Among the hydrocarbylaluminum compounds that canbe used as starting materials one can mention the trialkylaluminumcompounds, the triarylaluminum compounds, the dialkylaluminum hydrides,the diarylaluminum hydrides, the alkylarylaluminum hydrides, themonoalkylaluminum dihydrides, the monoarylaluminum dihydrides, and thelike. Illustrative thereof one can mention trimethylaluminum,triethylaluminum, tripropylaluminum, triisopropylaluminum,tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum,trioctylaluminum, tridecylaluminum, tridodecylaluminum,tribenzylaluminum, triphenylaluminum, trinaphthylaluminum,tritolylaluminum, dimethylaluminurn hydride, diisobutylaluminum hydride,dihexylaluminum hydride, didecylaluminum hydride, diphenylaluminumhydride, dixylylaluminum hydride, dinaphthylaluminum hydride,methylphenylaluminum monohydride, ethylnaphthylaluminum monohydride,methylaluminum dihydride, ethylaluminum dihydride, butylaluminumdihydride, isobutylaluminum dihydride, octylaluminum dihydride,dodecylaluminum dihydride, phenylaluminum dihydride, tolylaluminumdihydride, naphthylaluminum dihydride, and the like.

The poly(hydrocarbylaluminum oxides) can be prepared by slowly addingthe necessary amount of water to the hydrocarbylaluminum compound. Thisaddition of Water is carried out at a temperature of from about 0 C. toabout 0; preferably at a temperature of from about 10 C. to about 65 C.

The amount of water added to the hydrocarbylaluminum compound to producethe poly (hydrocarbylaluminum oxides) can be varied from about 0.25 moleto about 1.5

moles of water per mole of hydrocarbylaluminum compound with the rangeof from about 0.5 to about 1.25 more desirable. The preferred range,however, is from about 0.85 mole to about 1.05 moles of water per moleof hydrocarbylaluminum compound. While this range is preferred, thebroader range can be employed, but it has been found that when theamount of water employed is outside of the preferred range, thepoly(hydrocarbylaluminum oxide) produced is not as satisfactory aproduct for use as a catalyst component. It has also been found thatwhen an amount of water in excess of 1 mole is employed, some alumina isformed which either precipitates out of solution or forms a gel. It hasfurther been found that the most preferred range is from about 0.95 moleto about 1.05 moles of water per mole of hydrocarbylaluminum compound.

Among the transition metal compounds of the metals of Groups IVA, VA,and VIA which can be used as the second component of the catalystcompositions useful in this invention are the compounds of the metalstitanium, zirconium, hafnium, cerium, vanadium, niobium, tentalum,chromium, molybdenum, tungsten thorium and uranium. The suitablecompounds can be represented by the formula MX in which M represents thetransition metal atom X represents a halogen atom or an organic group,such as an alkoxy or ester radical, and n is the valence state of thetransition metal. Illustrative of some of the transition metal compoundswhich can be used one can mention, for example, vanadium dichloride,vanadium trichloride, vanadium tetrachloride, vanadium trifiuoride,vanadium tetrafiuoride, vanadium pentafluoride, vanadium triiodide,vanadyl chloride, titanium dibromide, titanium tribromide, titaniumtetrabromide, titanium dichloride, titanium trichloride, titaniumtetrachloride, titanium trifluoride, titanium tetrafiuoride, titaniumdiiodide, titanium tetraiodide, Zirconium dibromide, zirconiumtribromide, zirconium tetrabromide, zirconium dichloride, zirconiumtrichloride, Zirconium tetrachloride, zirconium tetrafiuoride, zirconiumtetraiodide, niobium pentabromide, niobium pentachloride, niobiumpentafluoride, tantalum pentabromide, tantalum pentachloride, tantalumpentafluoride, chromous bromide, chromic bromide, chromous chloride,chrornic chloride, chromous fluoride, chromic fluoride, molybdenumdibromide, molybdenum tribroinide, molybdenum tetrabromide, molybdenumdichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenumpentachloride, molybdenum hexafluoride, and the like. Among the organiccompounds of the transition metals one can mention chromium actate,chromium(III) oxy-2-ethylhexanoate, chromium(III) 2- ethylhexanoate,chromium(III) dichloroethylhexanoate, chromium(II) Z-ethylhexanoate,titanium(IV) 2-ethylhexanoate, zirconyl tetrabutoxide, chromium(III)isobutoxide, titanium tetraethoxide, dicyclopentadienyltitaniumdichloride, dicyclopentadienyltitanium difiuoride,dicyclopentadienylvanadium dichloride, zirconyl acetate, uranylbutyrate, vanadyl acetylacetonate, chromium acetylacetonate, zirconylacetylacetonate, and the like.

The third component of the catalyst complex when it is present is acompound represented by the formula:

MeR'

wherein R has the same meanings as defined above, Me is a metal from theGroups IA, IIA, or 11113, and x is an integer corresponding to thevalence of said metal. These compounds are well known to those skilledin the art.

The polymerization catalyst complex can be prepared by procedures knownto the art by adding the catalyst components to the inert, organicpolymerization solvent. In the preferred manner the catalyst mixture isprepared by first producing the poly(hydrocarbylaluminum oxide) in theform of a concentrated solution, taking a portion of this reactionmixture and further diluting it with diluent, adding the transitionmetal compound to this diluted mixture, and then adding this mixtureto asolution of the 4 third component the organo metallic compound of themetals of Groups IA, HA, and IIIB if the third component is to be used.

The inert organic diluents useful for the polymerization reaction arethe same diluents employed in producing the poly(hydrocarbylaluminumoxides). The polymerization of the mono-unsaturated alpha-olefins iscarried out by contacting the alpha-olefin with the mixture of thecatalyst complex in the inert diluent.

The composition of the catalyst complex is such that it contains fromabout 0.001 to about 0.05 millimole of the transition metal compound MXfrom about 0.2 to about 20 millimoles of the poly(hydrocarbylaluminumoxide); and, when present, from about 0.1 to about 2 millimoles of thecompound of the metals of Groups IA, IIA, and IIIB, per liter of inertdiluent. Preferably when it is present the concentration of the compoundof the metals of Groups IA, HA, and 11113 is kept as low as possible;and is dependent to some degree on the purity of the solvent, With purersolvents requiring smaller amounts. However, when a solvent is notemployed or the solvent is free of trace impurities which will destroythe effectiveness of the catalyst complex, this third component can andis preferably omitted. The mole ratio of the transition metal in thetransition metal compound to the aluminum in thepoly(hydrocarbylaluminum oxide) can be varied from 1:30 to about 1:800but is preferably from about 1:40 to 1:200.

By varying the ratios of the components used to produce the catalystcomplex and the components employed and by varying the temperature,pressure, and time of reaction, one can vary the properties of thepolyolefin produced.

The polymerization can be carried out at temperatures of from about 10C. or lower up to about 100 C., preferably at a temperature of fromabout 40 C. to about C. The pressure can be varied from subaltmo'sphericpressure, using an inert gas as diluent, to superatmospheric pressuresup to about atmospheres. Preferably, however, the reaction is carriedout at a pressure of about 5 to 30 atmospheres.

It has been found that a small amount of hydrogen present during thepolymerization has an effect upon the average molecular weight of thepolymer produced. In particular, the presence of hydrogen during thepolymerization serves to lower the average molecular weight of thepolymer formed.

Among the mono-unsaturated alpha-olefins which can be polymerized bythis invention are the mono-unsaturated aliphatic alpha-olefinscontaining from 2 to about 10 carbon atoms. Illustrative of thealpha-olefins which can be polymerized one can mention ethylene,propylene, butene-l, pentene-l, 3-methylbutene-1,'hexene-l,4-methylpentene-l, 3-ethylbutene-1, heptene-l, octene-l, decenel,4,4-dimethyl-l-pentene, 4-4,-diethyl-1-hexene, 3,4-dimethyl-l-hexene,and the like, and including within the definition the bicycloheptenessuch as bicyclohept-[2.2.l] ene and the hydrocarbyl derivatives thereof.The purity of the alpha-olefin feed may vary from about 94 percent toabout 100 percent; the only requirement is that the alpha-olefin be freeof impurities which would inactivate the catalyst. It is preferred,however, to use monomers of high purity in order to achieve greaterutilization of the catalyst.

The density of the polyolefins was determined according to the proceduredescribed by E. Hunter and W. G. Oaks, Trans. Faraday Society, 41, 49;the melt index Was determined according to the procedure described inASTM Dl23852T; and the flow rate was determined by the same procedureused to determine the melt index but employing a weight Which was either4.7 times as great or 10 times as great as that specified in the ASTMprocedure. The following examples further illustrate the process of thisinvention but are not to be construed as being limitative thereof.

Example 1 A clean, dry reaction flask was flushed with dry, oxy- 65Example 3 Ethylene was polymerized in a manner similar to that describedin Example 2. The catalyst composition consisted of 0.24 gram oftriisobutylaluminum, a portion geniree nitrogen and fitt d with a Serumcap: Ninety containing12mil11rnolesofpoly(1sobutyla1um1numoxide)milliliters of dry, oxygen-free heptane, which had been from Run G ofExample and @006 gram 'f m passed through a dry silica gel column andpurged with Z- Y Q a lyst mlXture W dry, oxygen-free nitrogen, wasinjected into the reaction allowed to age reaction flask for one hourfla k i a hypodermic Syringg An 3 portion f 10 C. under a dry nitrogenatmosphere before the addition triisobutylaluminum (40 millimoles) wassimilarly addof the ethylene monomer- Ethylene Was bubbled through ed Ahypodermic needle attached to a nitrogen line the catalyst for a totalperiod of about 76 minutes. The feed with a mineral oil bubbler wasinserted into the P01yethylene weighed 21.6 grams and it had a serum capto relieve pressure due to the isobutane evolved melt lndex P a e e anda flow Tate of 56 during the reaction. While continually agitating, 0.71fmma4-7 tunes determmatlonmilliliter of water (about 40 millimoles) wasslowly Example 4 added from a hypodermlc syringe at a temperature ofabout 45 C. and over a period of about 25 minutes. The Ethylene waspolymerized in a manner similar to that reaction product produced waspoly(isobutylaluminum described in Example 2, except that the heptanesolution oxide). Was heated to 40 C. after the triisobutylaluminum hadIn the same manner as described above, a series of been added to it, andthe temperature was raised to 60 reactions was carried out to produceadditional samples C. after the other catalyst components had beenadded. of the poly(hydrocarbylaluminum oxide) compounds. The catalystcomposition consisted of 0.08 gram of tri- For convenience, these runsare tabulated below, includisobutylaluminum, a portion containing 12millimoles of ing the run outlined above. poly(isobutylaluminum oxide)from Run G of Example 1 Volume, Weight, Milli- .Solvent Water MaximumRun Alkyl Milliliters grams moles Volume, Added, Tempera- MillilitersMillimoles ture 2 Started at 75, actual temperature range.

Example 2 A l-liter polymerization flask was equipped with a high speedstirrer, a gas inlet tube, a gas exit tube, a thermocouple well, anopening fitted with a serum cap, a liquid inlet tube, and a liquid exittube extending to the bottom of the flask. The equipment wasscrupulously cleaned and dried, and finally flushed with dry,oxygen-free nitrogen. A 500milliliter portion of pure, dry n-heptane,which had been passed through a silica gel column and stored over sodiumafter bubbling enough nitrogen through it to sweep out any entrainedoxygen, was added to the polymerization flask. The heptane was heated toC. and 0.35 gram of isobutylaluminum dichloride was injected by means ofa hypodermic syringe through the serum cap. Then 4 millimoles ofpoly(isobutylal=uminum oxide) obtained from Ron 1C above, and 0.47 gramof titanium tetrachloride were injected through the serum cap. Stirringwas stopped and the system was purged with about 0.2 cubic foot of pureethylene. Stirring was resumed and ethylene was bubbled through thereaction mixture for about 86 minutes. At the end of this time about 50milliliters of isopropanol was added and the polymer suspension wasfiltered. The filter cake was washed once with isopropanol and dried.Yield was 17.7 gramsof polyethylene having a melt index of 0.93 dgm. perminute, and a flow rate of 12.2 from a 4.7 times determination.

High molecular weight, solid polyethylene is produced under similarpolymerization conditions using a catalyst complex consisting of twocomponents only, poly(isobutylaluminum oxide) and titanium trichloride.

above, and 0.006 gram of chromium (III) 2-ethylhexanoate. Ethylene wasbubbled through for 60 minutes. The dried polyethylene had a melt indexof 0.61 dgm./ minute, and a flow rate of 48 from a 4.7 timesdetermination.

Example 5 Ethylene was polymerized in a manner similar to that describedin Example 4. The catalyst composition consisted of 0.24 gram oftriisobutylaluminurn, a portion containing 12 millimoles ofpoly(isobutylaluminum oxide) from Run G of Example 1, and 0.006 gram ofchromium (III) 2-ethylhexanoate. The dried polyethylene had a melt indexof 12.2 dgm./ minute, a flow rate of 229 from a 4.7 times determination,and a density of 0.9617 gram/cc.

Example 6 Ethylene was polymerized in a manner similar to that describedin Example 4. The catalyst composition consisted of 0.4 gram oftriisobutylaluminum, a portion contaming 12 millimoles ofpoly(isobutylal-uminum oxide) from Run G of Example 1, and 0.006 gram ofchromium(III) Z-ethylhexanoate. Ethylene was bubbled through Forconvenience, all of the experiments are tabulated below:

Triisobutyl- Poly(isobuty1- Chromium 'Jomp- Melt In- Run aluminum,aluminum Compound, ature, Time, Yield, dex, Flow* grams oxide) grams 0.minutes grams dgmJmin. Rate millimoles 0. 56 a 3. 2 0. 25 82-103 5 39. 80. 4 a 1. 6 0. 05 65-101 7. 5 30. 5 2.35 56. 0. 32 b 0. 8 0. 03 62*7012. 13. 5 0. 054 1. 08 0. 24 b 0. 6 0. 02 8087 20. 0 0.23 4. 8 0.2 b 1.00.011 71 20 21. 5 0.037 0.90 0. 5G a 1.6 0. 03 64-07 10 31. 5 1. 44 34.0 0. 28 c 1 0. 016 66-103 4 34. 6

a From Run A of Example 1. b From Bun B of Example 1. c From Run 0 01'Example 1. d Chr0mium(II1) acetate was used 111 this experiment. 4.7times determination.

the catalyst mixture for about 117 minutes. The solid Example 11polyethylene weighed 31.3 grams after drying.

Example 8 Ethylene was polymerized in a manner similar to that describedin Example 4. The catalyst composition consisted of 0.5 gram oftridodecylaluminum, a portion containing 12 millimoles ofpoly(isobutylaluminum oxide) from Run G of Example 1, and 0.006 gram ofchromiurn(III) 2-ethylhexanoate. The dried polyethylene weighed 14.7grams, and it had a melt index of 0.37 dgm./ minute, and a flow rate offrom a 4.7 times determination.

Example 9 Ethylene was polymerized in a manner similar to that describedin Example 4. The catalyst composition consisted of 0.24 gram oftriisobutylaluminum, a portion containing 12 millimoles ofpoly(isobutylaluminum oxide) from Run G of Example 1, and 0.006 gram ofchromium(II) 2-ethylhexanoate. The dried polyethylene weighed 30.7grams, and it had a melt index of 2.37 dgrn./ minute, and a flow rate of105 from a 4.7 times determination.

Example 10 A stainless steel autoclave, equipped with a gas tube fittedwith a serum cap, was flushed with dry nitrogen and 250 milliliters ofdry n-heptane was added. A 0.56 gram portion of triisobutylaluminum wasadded through the serum cap using a hypodermic syringe. Thetriisobutylaluminum was washed down with a small portion of dry heptane.A portion containing 3.2 millimoles of poly(isobutylaluminum oxide) fromRun A of Example 1 was added and washed into the autoclave in a similarmanner. The contents of the autoclave were then agitated for about oneminute and then a mixture of 0.25 gram of chromiumfill)oxy-2-ethylhexanoate in n-heptane was added and washed into theautoclave with suflicient nheptane to give a total volume of 500milliliters of nheptane. The mixture was stirred and heated to 60 C. to70 C. The pressure was released, and the system was then pressurized to400 p.s.i.g. ethylene pressure. Ethylene was bubbled through thecatalyst composition suspended in the solvent at a temperature of from82 C. to 103 C. for a period of about 5 minutes. The contents were thencooled to room temperature and isopropanol was added to quench thecatalyst complex. The slurry was filtered and the polyethylene filtercake was washed once with isopropanol. The dried polyethylene weighed39.8 grams.

A series of experiments was carried out in the same manner as describedabove but varying the composition of the catalyst complex, thetemperature, and the time.

Ethylene was polymerized in a manner similar to that described inExample 10, at a pressure of 100 p.s.i.g. The catalyst compositionconsisted of a 4 milliliter portion of the poly(isobutylaluminum oxide)reaction product from Run J of Example 1, and 3.6 mgm. of vanadiumtetrachloride. After a 5 minute reaction period there was obtained 7.3grams of polyethylene.

The substitution of chromium acetylacetonate for the vanadiumtetrachloride, in equivalent amount, also produces a catalyst complexthat polymerizes ethylene to high molecular weight solid polyethylene.

Example 12 Ethylene was polymerized in a manner similar to thatdescribed in Example 11. The catalyst composition consisted of 0.24 gramof triisobutylaluminum, 5 mgrn. of titanium(IV) 2ethylhexanoate, and a 4milliliter portion of the poly(isobutylaluminum oxide) reaction productfrom Run J of Example 1. Solid polyethylene was recovered after a onehalf hour reaction period.

Example 13 Ethylene was polymerized in a manner similar to thatdescribed in Example 10, at a temperature of 73 C. to C. and a pressureof 400 p.s.i.g. The catalyst composition consisted of 0.05 gram ofzirconyl acetate, 0.4 gram of triisobutylaluminum, and a 5 milliliterportion of the poly(isobutylaluminum oxide) reaction product from Run Bof Example 1. After a 25 minute reaction period, 5.7 grams of solidpolyethylene was recovered.

Example 14 Ethylene was polymerized in a manner similar to thatdescribed in Example 10, at a temperature of 74 C. to 92 C. and apressure of 400 p.s.i.g. The catalyst composition consisted of 0.8 gramof triisobutylaluminum, 0.05 gram of uranyl butyrate, and a 3 milliliterportion of the poly(isobutylaluminum oxide) reaction product from Run Aof Example 1. At the end of a 20 minute reaction, there was obtained 11grams of polyethylene.

Example 15 In a similar manner, butene-l is polymerized to producepoly(butene1).

the autoclave was maintained at 100 p.s.i.g. For conven ience, theexperiments are tabulated below:

Triisobutyl- Poly(isobutyl- Chromium Temper- Melt In- Run aluminum,aluminum Compound, ature, Time, Yield, dex, Flow* grams oxide), grams C.minutes grams dgm./min. Rate millimoles 0. 24 b 4. 0 0. 002 66 72 30 0.24 E 4.0 i 0. 004 70-76 32 B 0. 12 c 4.0 0. 002 6668 18 0. 24 B 1.0 i0.002 68-72 35 0. 24 c 2.0 f 0. 002 74-76 31 0. 24 d 5.0 f 0. 002 64-7648 0. 24 d 4. 0 i 0.002 68-86 30 0. 2 9 2.0 c 0.002 68-83 0. 08 c 2.0 B0. 002 70 92 16 E 2.0 8 0 002 70-80 30 0. 24 b 3. 0 0. 001 66-74 38Triethylaluminum was used in this experiment. From Run E of Example 1. cFrom Run G of Example 1. d From Run H of Example 1. 9 From Run 0 ofExample 1. f Chromium (III) oxy-2-ethylhexoatc. s Chromium (II)2-ethylhexoate. h Chromium (III) acetate. *4.7 times determination.Example 16 Example 19 (I) A one liter stainless steel autoclave wasflushed with nitrogen and charged with 500 milliliters of anhydrousheptane, 0.16 gram of t'riisobutylaluminum, 0.8 millimole ofpoly(isobutylaluminum oxide), and 500 milliliters of gaseous hydrogen.The autoclave was sealed, heated to 70 C., and pressurized to 100p.s.i.g.

with ethylene. A solution of 2 mgm. of chromium(III) 2-ethylhexanoate in20 milliliters of heptane was added to start the reaction. After 29minutes at 70 C. and 100 p.s.i.g. of ethylene, the autoclave was cooledand vented. The contents were filtered and the polyethylene was washedwith isopropanol and dried. The polymer had a melt index of 6.5dgm./minute, a flow rate of 500 from the 10 times determination, astiffness of 153,000 p.s.i., a density of 0.9638 g./cc., and 15.8percent Wax.

(II) When the reaction was repeated in the absence of hydrogen, therewas obtained 44 grams of polyethylene after 47 minutes. This polymer hada melt index of 1.2 dgm./minute, a flow rate of 153, a stiffness of149,000 p.s.i., a density of 0.9614 g./cc., and 16.9 percent wax.

Example 17 In a manner similar to that described in Example 10, ethylenewas polymerized at a temperature of 70C. to 75 C. and a pressure of 100p.s.i.g. The catalyst consisted of 0.064 gram of triisobutylaluminum,0.2 millimole of poly(isobutylaluminum oxide) and 4 mgm. ofchromium(III) Z-ethylhexanoate. Eight hundred milliliters of hydrogengas was introduced before heating and before the addition of thechromium(IlI) 2-ethylhexanoate. After a 32 minute reaction there wasobtained 26 grams of solid polyethylene having a melt index of 1.1 dgm.per minute, a flow rate of 67 from a 10 times determination, a stiffnessof 132,000 p.s.i., a density of 0.9527 g./cc., and 2.3 percent wax.

Example 18 A copolymer of ethylene/butene-l was produced in a mannersimilar to that described in Example 16(1). The catalyst compositionconsisting of 0.08 gram of triisobutylaluminum, 0.4 millimole ofpoly(isobutylaluminum oxide), and 4 mgm. of chromium(III)2-ethylhexanoate. The monomers mixture contained 3 mole percentbutene-l. After reacting for 63 minutes at 70 C. to 74 C. and a pressureof 100 p.s.i.g., there was obtained 44 grams of the copolymer, having amelt index of 0.19 dgm. per minute, a flow rate of 37.1 from a 10 timesdetermination, a density of 0.9497 g./cc., a stiffness of 110,000p.s.i., and 27.1 percent wax. The wax, as in all instances, could beremoved by solution in boiling cyclohexane.

Example 20 A one liter stainless steel autoclave was flushed withnitrogen and charged with 500 milliliters of anhydrous heptane and 0.08gram of triisobutylaluminum. The autoclave was sealed, heated to 70 C.and pressurized to 100 p.s.i.g. with a mixture of ethylene containing 3mole percent butene-l. Then a mixture of 4 mgm. of chromium- (III)Z-ethylhexanoate and 0.2 millimole of poly(isobutylaluminum oxide) whichhad been aged overnight was pressured into the autoclave. After 21minutes at 70 C. to 74 C. and a pressure of 100 p.s.i.g., there wasobtained 21 grams of a copolymer of ethylene/butene-l having a meltindex of 0.01 dgm./minute, a flow rate of 4.8 from a 10 timesdetermination, a density of 0.9483 g./cc., a stillness of 110,000p.s.i., and 5 percent wax.

Example 21 Ethylene was polymerized in a manner similar to thatdescribed in Example 19 except that the catalyst composition was free oftriisobutylaluminum and consisted of two components only, thepoly(isobutylaluminum Ethylene was polymerized in a manner similar tothat xide) and the chr0mium(III) 2-ethylhexanoate The described above inExample 10 except that the pressure in experiments are tabulated below:

Poly(isobutyl- Chromium Prcs- Temper- Melt Run aluminum, compound, sure,ature, Time, Yield, Index, Density,

oxide) millimicromolcs p.s.i.g. 0. minutes grams dgm/ g/cc.

moles min.

3. 2 76 400 -97 12 34.6 3. 2 76 375 east 15 1o. 0 0. e 5 100 -78 70 56.30. 03 0. 9491 2 10 70 69 41. 5 0. 05 0. 9459 2 10 7074 63 40. 0 0. 06 0.9475 6 10 100 70 46 23. 5 0. 15 0. 9536 0. 8 10 100 70 47 21. 5 0. 17 0.9620 a Hydrogen present. b Ethylene-butene feed.

\1 Ethylene-butene-hydrogen feed.

9 Isobutylene present.

As is well known the melt index of the polymer is a measure of themolecular weight of the resin and is inversely proportional thereto. Themelt indices of the polyolefins produced by the processes of thisinvention can vary over a wide range from as low as a value of to ashigh as 1000 dgm./minute, or higher. The density of the polyolefins canbe varied. Thus, for example, the density of polyethylene can vary fromabout 0.93 to about 0.975 gram/cc. Generally, however, the polyethylenepolymers produced by the processes of this invention have a densityrange from about 0.94 to about 0.96 gram/cc.

The amount of polymeric material formed which is soluble in boilingcyclohexane is affected by the excess present of the compounds of themetals of Groups IA, IIA, or IIIB; the total concentration of thecatalyst complex; the presence of small amounts of other olefiniccompounds; and by the presence of other impurities in the startingmaterials. Thus, constant control of these factors is desirable to keepthe formation of cyclohexane soluble materials at a minimum.

The melt index of the polyolefins produced With the catalystcompositions of this invention can be controlled by controlling thepolymerization temperature, since it was found to be affected veryreadily by changes in temperature. Thus, for example, the melt index ofpolyethylene has been shown to increase from 0.2 dgm./minute to 2.0dgm./minute as the polymerization temperature was increased from 67 C.to 74 C.

The polymerization rate has also been found to be alfected by the moleratio of water to organo hydrocarbylaluminum compoun-d used in preparingthe poly(hydrocarbylaluminum oxide) component of the catalystcomposition. It was found that optimum polymerization rate is achievedwhen the mole ratio of water to organo hydrocarbylaluminum compound isat about 1:1. Polymerization rates as high as 90,000 grams ofpolyethylene per millimole of transition metal per hour have beenobserved.

As is obvious to the ordinary scientist skilled in the art the processesof this invention can be carried out in a continuous manner or in abatchwise manner.

What is claimed is:

1. A polymerization catalyst comprising the product formed by reactingpoly(hydrocarbylaluminum oxide) and a transition metal compound selectedfrom the group consisting of the compounds of the metals of Groups IVA,VA, and VIA of the formula MX wherein M represents the transition metalatom, X is a member selected from the group consisting of a halogen atomand an organic group, and n is the valence state of the transitionmetal, said poly(hydrocarbylaluminum oxide) being the product of thereaction of from 0.25 to 1.5 mole of water per mole of organohydrocarbylaluminum compound wherein the hydrocarbyl moiety thereof isselected from the group consisting of an alkyl radical containing from 1to about 12 carbon atoms and an aryl radical selected from the groupconsisting of phenyl and naphthyl radicals.

2. A polymerization catalyst comprising the product formed by reacting apoly(hydrocarbylaluminum oxide), a transition metal compound selectedfrom the group consisting of the compounds of the metals of Groups IVA,VA, and VIA of the formula MX wherein M represents the transition metalatom, X is a member selected from the group consisting of a halogen atomand an organic group, and n is the valence state of the transitionmetal, and a compound selected from the group consisting of thecompounds of the metals of Groups IA, IIA, and H113, represented by theformula MeR' wherein R represents a member selected from the groupconsisting of an alkyl radical having from 1 to about 12 carbon atoms,an aryl radical, and a hydrogen atom, Me represents said metal, and x isan integer corresponding to the valence of said metal, saidpoly(hydrocarbylaluminum oxide) being the product of the reaction offrom 0.5 to 1.25 mole of water per mole of organo hydrocarbylaluminumcompound wherein the hydrocarbyl moiety thereof is selected from thegroup consisting of an alkyl radical containing from 1 to about 12carbon atoms and an aryl radical selected from the group consisting ofphenyl and naphthyl radicals.

3. A polymerization catalyst comprising the product formed by reactingpoly(hydrocarbylaluminum oxide) and a transition metal compound selectedfrom the group consisting of the compounds of the metals of Groups IVA,VA, and VIA of the formula MX wherein M represents the transition metalatom, X is a member selected from the group consisting of a halogen atomand an organic group, and n is the valence state of the transitionmetal, said poly(hydrocarbylaluminum oxide) being the product of thereaction of from 0.5 to 1.25 mole of water per mole of organohydrocarbylaluminum compound wherein the hydrocarbyl moiety thereof isselected from the group consisting of an alkyl radical containing from 1to about 12 carbon atoms and an aryl radical selected from the groupconsisting of phenyl and naphthyl radicals.

4. A polymerization catalyst comprising the product formed by reacting apoly(hydrocarbylaluminum oxide) containing units represented by thegeneral formula:

wherein R represents a member selected from the group consisting of analkyl radical containing from 1 to about 12 carbon atoms and an arylradical selected from the group consisting of phenyl and naphthylnuclei, a transition metal compound selected from the group consistingof the compounds of the transition metals of Groups IVA, VA, and VIA ofthe formula MX wherein M represents the transition metal atom, X is amember selected from the group consisting of a halogen atom and anorganic group, and n is the valence state of the transition metal, and acompound selected from the group consisting of the compounds representedby the formula:

MeR'

wherein R' represents a member selected from the group consisting of analkyl radical containing from 1 to about 12 carbon atoms, an arylradical, and a hydrogen atom, Me is a metal selected from the groupconsisting of the metals of Groups IA, IIA, and IIIB, and x is aninteger corresponding to the valence of said metal, said poly(hydrocarbylaluminum oxide) being the product of the reaction of thereaction of from 0.85 to 1.05 mole of water per mole of organohydrocarbylaluminum compound.

5. A polymerization catalyst comprising the product formed by reacting apoly(hydrocarbylaluminum oxide) containing units represented by thegeneral formula:

R ital wherein R represents a member selected from the group consistingof an alkyl radical containing from 1 to about 12 carbon atoms and anaryl radical selected from the group consisting of phenyl and naphthylnuclei, and a transition metal compound selected from the groupconsisting of the compounds of the transition metals of Groups IVA, VA,and VIA of the formula MX wherein M represents the transition metalatom, X is a member selected from the group consisting of a halogen atomand an organic group, and n is the valence state of the transi tionmetal, said poly(hydrocarbylaluminum oxide) being the product of thereaction of from 0.85 to 1.05 mole of water per mole of organohydrocarbylaluminum compound.

6. A polymerization catalyst comprising the product formed by reactingpoly(isobutylaluminum oxide), triisobutylaluminum, and chromium(III)Z-ethyl-hex-anoa-te,

13 said poly(isobutylaluminum oxide) being the product of the reactionof from 0.85 to 1.05 mole of Water per mole of isobutylaluminum.

7. A polymerization catalyst comprising the product formed by reactingpoly(isobutyaluminum oxide), triisobutylaluminum, and chromiurnfll)Z-ethylhexanoate, said poly(isobutylaluminum oxide) being the product ofthe reaction of from 0.85 to 1.05 mole of water per mole ofisobutylaluminum.

8. A polymerization catalyst comprising the product formed by reactingpoly(isobutylaluminum oxide) triisobutylaluminum, and chromium IIIoxy-2-ethylhexanoate, said poly(isobutylaluminum oxide) being theproduct of the reaction of from 0.85 to 1.05 mole of water oer mole ofisobutylaluminum.

9. A polymerization catalyst comprising the product formed by reactingpoly(isobutylaluminum oxide), triisobutylaluminum, and titanium IV2-ethylhexanoate, said poly(isobutylaluminum oxide) being the product ofthe reaction of from 0.85 to 1.05 mole of water per mole ofisobutylaluminum.

10. A polymerization catalyst comprising the product formed by reactingpoly(isobutylaluminum oxide), triisobutylaluminurn, and zirconiumacetate, said poly(isobutylaluminum oxide) being the product of thereaction of from 0.85 to 1.05 mol of Water per mole of isobutylaluminum.

11. A polymerization catalyst comprising the product formed by reactingpoly(isobutylalurninum oxide), isobutylaluminum dichloride, and titaniumtetrachloride, said poly(isobuty1aluminum oxide) being the product ofthe reaction of from 0.85 to 1.05 mole of water per mole ofisobutylaluminum.

12. A polymerization catalyst comprising the product formed by reactingpoly(isobutylaluminum oxide), tridodecylaluminum, and chromium IIIZ-ethylhexanoazte, said poly(isobutylaluminum oxide) being the productof the reaction of from 0.85 to 1.05 mole of water per mole ofisobutylaluminum.

13. A polymerization catalyst comprising the product formed by reactingpoly(isobutylaluminum oxide) and titanium trichloride, saidpoly(isobutylaluminum oxide) being the product of the reaction of from0.85 to- 1.05 mole of water per mole of isobutylaluminum.

14. A polymerization catalyst comprising the product formed by reactingpoly(isobutylaluminum oxide) and vanadium tetrachloride, saidpoly(isobutylaluminum oxide) being the product of the reaction of from0.85 to 1.05 mole of water per mole of isobutylaluminum.

15. A polymerization catalyst comprising the product formed by reactingpoly(isobu-tylaluminum oxide) and chromium III Z-ethylhexanoate, saidpoly(isobutylaluminum oxide) being the product of the reaction of from0.85 to 1.05 mole of water per mole of isobutylaluminum.

16. A polymerization catalyst comprising the product formed by reactingpoly(isobutylaluminum oxide) and chromium acetylacetonate, saidpoly(isobutylaluminum oxide) being the product of the reaction of said0.85 to 1.05 mole of water per mole of isobutylaluminum.

References Cited by the Examiner UNITED STATES PATENTS 3,135,705 6/1964Vandenbcrg 260-2 3,152,105 10/1964 Long 260-94.9

FOREIGN PATENTS 2,984,658 5/1961 Germany.

TOBIAS E. LEVOW, Primary Examiner.

1. A POLYMERIZATION CATALYST COMPRISING THE PRODUCT FORMED BY REACTINGPOLY (HYDROCARBYLALUMINUM OXIDE) AND A TRANSISTION METAL COMPOUNDSELECTED FROM THE GROUP CONSISTING OF THE COMPOUNDS OF THE METALS OFGROUPS IVA, VA, AND VIA OF THE FORMULA MXN WHEREIN M REPRESENTS THETRANSITION METAL ATOM, X IS A MEMBER SELECTED FROM THE GROUP CONSISTINGOF A HALOGEN ATOM AND AN ORGANIC GROUP, AND N IS THE VALENCE STATE OFTHE TRANSITION METAL, SAID POLY (HYDROCARBYLALUMINUM OXIDE) BEING THEPRODUCT OF THE REACTION OF FROM 0.25 TO 1.5 MOLE OF WATER PER MOLE OFORGANO HYDROCARBYLALUMINUM COMPOUND WHEREIN THE HYDROCARBYL MOIETYTHEREOF IS SELECTED FROM THE GROUP CONSISTING OF AN ALKYL RADICALCONTAINING FROM 1 TO ABOUT 12 CARBON ATOMS AND AN ARYL RADICAL SELECTEDFROM THE GROUP CONSISTING OF PHENYL AND NAPHTHYL RADICALS.
 2. APOLYMERIZATION CATALYST COMPRISING THE PRODUCT FROMED BY REACTING A POLY(HYDROCARBYLALUMINUM OXIDE), A TRANSITION METAL COMPOUND SELECTED FROMTHE GROUP CONSISTING OF THE COMPOUNDS OF THE METALS OF GROUPS IVA, VA,AND VIA OF THE FORMULA MXN WHEREIN M REPRESENTS THE TRANSITION METALATOM, X IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HALOGEN ATOMAND AN ORGANIC GROUP, AND N IS THE VALENCE STATE OF THE TRANSITIONMETAL, AND A COMPOUND SELECTED FROM THE GROUP CONSISTING OF THECOMPOUNDS OF THE METALS OF GROUPS IA, IIA, AND IIIB, REPRESENTED BY THEFORMULA MER''X, WHEREIN R'' REPRESENTS A MEMBER SELECTED FROM THE GROUPCONSISTING OF AN ALKYL RADICAL HAVING FROM 1 TO ABOUT 12 CARBON ATOMS,AND ARYL RADICAL, AND A HYDROGEN ATOM, ME REPRESENTS SAID METAL, AND XIS AN INTEGER CORRESPONDING TO THE VALENCE OF SAID METAL, SAID POLY(HYDROCARBYLALUMINUM OXIDE) BEING THE PRODUCT OF THE REACTION OF FROM0.5 TO 1.25 MOLE OF WATER PER MOLE OF ORGANO HYDROCABYLALUMINUM COMPOUNDWHEREIN THE HYDROCARBYL MOIETY THEREOF IS SELECTED FROM THE GROUPCONSISTING OF AN ALKYL RADICAL CONTAINING FROM 1 TO ABOUT 12 CARBONATOMS AND AN ARYL RADICAL SELECTED FROM THE GROUP CONSISTING OF PHENYLAND NAPHTHYL RADICALS.